Organoaluminum halides and their preparation

ABSTRACT

Organoaluminum halides in which the aluminum atom carries a substituted allylcarbinyl group or a substituted cyclopropylcarbinyl group are formed by reacting an aluminacyclopent-3-ene moiety with a primary aliphatic monohalide. The resultant organoaluminum halides are versatile intermediates. Hydrolysis yields substituted 1-alkenes and ring substituted methylcyclopropanes, respectively. Novel classes of substituted cyclopropanes are producible in this manner.

United States Patent 1 June 13, 1972 Shepherd, Jr.

[ ORGANOALUMINUM HALIDES AND THEIR PREPARATION [72] Inventor: Lawrence H. Shepherd, Jr., Baton Rouge,

[73] Assignee: Ethyl Corporation, New York, NY.

[22] Filed: July 2, 1970 21 App]. No.2 52,077

52 us. c1. ..260/448 A, 260/612, 260/650, 260/666, 260/668 51 1111.01. ..c07r 5/06 [58] Field 61 Search ..260/448 A [56] References Cited UNITED STATES PATENTS 2,906,763 9/1959 McKinnis ..260/448 A 3,028,408 4/1962 Redman 8t 81. ..26o/448 A 3,064,027 1 1/1962 Kl'eider 61 al. ...260/448 A 3,100,219 8/1963 KOSICI' 61 a] ...260/448 A 3,260,730 7/1966 Hubel 61 61.... ..260/448 A x 3,325,524 6/1967 Lundeel'l ..26o/448 A 3,328,447 6/1967 Kottenhahn ..260/448 A 3,391,208 7/1968 Marcus 6161 ...260/448 A x 3,426,052 2/1969 Hubel 6161 ..260/448 A x 3,493,623 2/1970 Br6nd61 ..260/448 A x FOREIGN PATENTS OR APPLICATIONS 3 8 1 80 9/1963 Japan ..260/448 A Primary Examiner-Tobias E. Levow Assistant Examiner-H. M. S. Sneed Atromey-Donald L. Johnson, John F. Sieberth and Arthur G. Connolly [57] ABSTRACT 41 Claims, N0 Drawings ORGANOALUMINUM HALIDES AND THEIR PREPARATION This invention relates to novel and useful organo aluminum halides, their synthesis, and their use in the synthesis of a variety of useful end products. This invention also relates to the novel and useful end products producible via the technology of this invention. Other aspects, advantages, features, and embodiments of this invention will be apparent from the ensuing description and appended claims.

BACKGROUND In copending application Ser. No. 771,651, filed Oct. 29, 1968, now [1.8. Pat. No. 3631065, it is shown that nonionic organoaluminum compounds possessing an aluminacycloalkene moiety are produced by causing interaction among aluminum, a conjugated diene and a hydrocarbon aluminum hydride in the presence of a Lewis base capable of complexing with the nonionic organoaluminum compound without undergoing excessive cleavage. For example, when the diene reactant is butadiene or butadiene substituted in the two position or in the two and three positions, the principal product is characterized by the formula:

wherein R is a hydrocarbon group having up to about 18 carbon atoms, R is a hydrogen, alkyl or alkenyl group, and R is a hydrogen or alkyl group.

Another method for producing the nonionic organoaluminum compounds possessing an aluminacycloalkene moiety is set forth in copending application Ser. No. 822,046, filed May 5, 1969. According to that process such compounds are produced by causing interaction among aluminum, a conjugated diene, an alkali metal aluminum tetrahydrocarbyl and hydrogen, the reaction being conducted in the presence of a Lewis base capable of complexing with the nonionic organoaluminum compounds without undergoing excessive cleavage. For example, when using, in this reaction, butadiene or butadiene substituted in the two position, or in the two and three positions, the principal product is characterized by the fonnula set forth above.

THE INVENTION Among the discoveries involved in the present invention is the finding that on reacting an organoaluminum compound containing an aluminacycloalkene moiety, notably an aluminacyclopent-3-ene moiety (see the above referred to copending applications) with a primary hydrocarbyl monohalide, new organoaluminum compounds are produced. One class of compounds producible in this manner is an organoaluminum compound having bonded to an aluminum atom a halogen atom and an allylcarbinyl group of the formula:

wherein R, R and R" are the same ordifferent and are hydrogen or hydrocarbyl groups.

Another type of compound producible by the foregoing reactionis an organoaluminum compound having bonded to an aluminum atom a halogen atom and a cyclopropylcarbinyl group of the formula:

wherein R, R and R" are the same or different and are hydrogen or hydrocarbyl groups.

A further feature of this invention is the discovery that although both of the foregoing classes of compounds tend to be formed as coproducts of the reaction, it is possible to influence the relative proportions thereof by proper selection of the halogen atom present in the primary aliphatic monohalide reactant. Thus, when it is desired to provide a product enriched in the allylcarbinyl substituted compounds, the halogen atom of the monohalide reactant is preferably chlorine. If, on the other hand, it is desired to produce a product enriched in the organo aluminum halide containing the cyclopropylcarbinyl group, it is desirable that the halogen atom of the halide reactant be bromine.

It will thus be seen that this invention provides inter alia, two general classes of novel organoaluminum halides--those carrying a substituted allylcarbinyl group and those carrying a substituted cyclopropylcarbinyl group. Also, through proper selection of the primary aliphatic monohalide reactant, the invention makes it possible to have either product predominate over the other.

The foregoing embodiments of this invention may be represented by the following equations:

In the above equations a1 represents two-thirds of a chemical equivalent of aluminum, the groups designated by R may be the same or different and are hydrogen or hydrocarbyl groups (preferably hydrogen or lower alkyl groups), the group designated as R is hydrogen or a suitable organic radical and X is halogen, preferably chlorine, bromine or iodine. In this connection, the third bond of the aluminum atom is satisfied by an innocuous substituent--i.e., a group which does not prevent the specified reaction(s) from occurring. Based on the present state of the art, this innocuous substituent will more often be a hydrocarbyl group or a hydrocarbyl aluminum group, although it is entirely possible that other groups such as halogen, alkoxy or other innocuous groups could be present. As explained in the copending applications referred to above, all disclosures of which are incorporated herein as if fully set forth in this specification, the available experimental evidence tends strongly to indicate that when forming the organoaluminum compounds containing an aluminacyclopent-Ii-ene moiety, the third bond of the aluminum is satisfied by a hydrocarbyl group corresponding to the hydrocarbon group(s) present in either the hydrocarbon aluminum hydride or the alkali metal aluminum tetrahydrocarbyl used in its synthesis. For example, if the compound containing the aluminacyclopent-3-ene moiety involves diisobutylaluminum hydride in its synthesis, the third bond of the aluminum in the product would be satisfied for the most part by an isobutyl group. By the same token, if sodium aluminum tetraethyl is used in the synthesis reaction, the organo aluminum compound containing the aluminacyclopent-3-ene moiety would ,have the third bond of the aluminum atom satisfied in the 1 main by an ethyl group.

Ofir wherein R is a hydrogen, alkyl or alkenyl group; and R is a hydrogen or alkyl group.

For all practical purposes, therefore, the identity of the innocuous group satisfying the third valence bond of the aluminum atom in the aluminacyclopent-3-ene moiety is of academic interest only. Any group which does not interfere with the desired reactions of this invention can be present inasmuch as the reactions themselves are focused upon the aluminacyclopent-3-ene moiety itself. The remainder of the molecule, if innocuous in the sense referred to above, can be considered excess baggage. The same considerations apply to the group satisfying the third valence bond of the aluminum in the organoaluminum halides of this invention-usually this group will correspond to the group present on the aluminum atom of the aluminacyclopent-3-ene reactant.

It will be apparent from the above equations that if the groups designated by R on the aluminacyclopent-3-ene moiety are the same (e.g., they are both hydrogen or they are the same alkyl or alkenyl group), there will be but one isomer of the product involving paths a and b. If on the other hand the two R groups differ from each other, there is the tendency for two isomers of each respective product to be formed, this depending upon which of the two allylic carbon atoms of the aluminacyclopent-3-ene participated in the reaction. As a general rule the allylic carbon atom which is least hindered sterically is the favored site of the reaction. By way of example, if one of the groups designated by R is a methyl group and the other R group is hydrogen, the allylic carbon atoms carrying the hydrogen atom participate in the reaction to a greater extent than the allylic carbon atoms carrying the methyl group, although isomers corresponding to both interactions are formed in the reaction product.

As a general proposition the preferred allylcarbinyl organoaluminum halides of this invention are those in which the halogen atom is chlorine. In the case of the organoaluminum compounds of this invention containing a substituted cyclopropyl carbinyl group, the halogen atom is preferably bromine. It will be seen that these preferred compounds are producible in high yield from readily available and inexpensive primary aliphatic monohalides. It will be recalled that the use of primary hydrocarbyl monochlorides in the reaction tends to favor the formation of the compounds containing the substituted allylcarbinyl group, whereas the use of primary hydrocarbyl monobromides tends to favor formation of the compounds containing the substituted cyclopropylcarbinyl group. In other words, in the equation presented above, if X is chlorine, reaction via route a is enhanced. On the other hand, if X is bromine, reaction via course b is favored.

The organoaluminum halides of this invention are particularly useful as intermediates for the synthesis of other compounds. For example, one aspect of this invention involves the hydrolysis of these compounds in order to produce substituted l-alkenes:

or ring substituted methylcyclopropanes:

wherein R, R and R are the same or different and are hydrogen or suitable organic groups such as hydrocarbyl groups. It will, of course, be understood that both types of these compounds may be readily formed by hydrolyzing a mixture of both types of organoaluminum halides of this invention.

Thus, in another of its embodiments this invention provides a process of producing a substituted olefin or a substituted cyclopropane, or both, which comprises reacting an organoaluminum compound containing an aluminacyclopent-fiene moiety with a primary aliphatic monohalide (preferably one in which the halogen atom is chlorine, bromine or iodine) and hydrolyaing the organoaluminum halide product so obtained.

Another remarkable feature of this invention is the discovery that the temperature of the hydrolysis reaction oflen afiects the relative proportions of the substituted l-alkenes and ring substituted methylcyclopropanes produced. In particular, it has been discovered that when hydrolyzing a given system containing both types of organoaluminum halides of this invention (Le. a compound containing the allylcarbinyl group and a compound containing the corresponding cyclopropylcarbinyl group), hydrolysis at low temperatures tends to promote an increased proportion of the substituted 1- alkene relative to the ring substituted methylcyclopropane. 0n the other hand, hydrolysis at higher temperatures tends to promote an increased proportion of the ring substituted methylcyclopropane relative to the substituted l-alkene. Thus, another embodiment of this invention involves producing a substituted olefin or a substituted cyclopropane, or both, by reacting an aluminacyclopent-3-ene moiety with a primary aliphatic monohalide and hydrolyzing the organoaluminum halide product so obtained at a temperature sufficiently low to enhance the proportion of the substituted olefin relative to the substituted cyclopropane. Still another embodiment of this invention involves carrying out this same process wherein the hydrolysis is effected at a temperature sufficiently high to enhance the proportion of the substituted cyclopropane relative to the substituted olefin.

The foregoing reactions provide the art with two classes of cyclopropane derivatives for which no synthesis was apparently known heretofore. One such class of compounds is a substituted cyclopropane having the formula:

Cat Haw H2 (IV) wherein R and R" are the same or different and are hydrogen, alkyl or alkenyl groups, and R R and R are the same or different and are hydrogen, halogen, alkyl, alkenyl, cycloalkyl, aryl or alkoxy groups. The allyl substituted cyclopropanes of formula (III) above can be readily polymerized with ethylene, propylene, combinations of ethylene and propylene, and with other alpha-olefin monomers to produce high molecular weight polymers having novel and useful properties. The technology for effecting such polymerizations is well known to those skilled in the art and is based upon the original discoveries by Ziegler and his colleagues and Natta and his colleagues. In addition, these compounds may be used as or converted into insecticides, germicides and fungicides. The cyclopropanes depicted by formula (IV) above may be used as insecticides, fungicides, bactericides, miticides, watermark detecting agents, and as special 5 purpose solvents where the combination in the same molecule of cycloparafi'inicity and aromaticity is of advantage.

As noted above the hydrolysis of the organoaluminum halide compounds of this invention makes possible the synthesis of a very large number of end products. Some appreciation of 10 i the products which may be readily obtained in this manner TABLE Alumina cyclopeut- Primary aliphatic monohalide 3-ene moiety reactant alCl CHz-CH-CH-CH3 i ilCl CH2 i: n-CaHnI all CH2CH-CH (CHzhCHa alBr alBr

2 CHgCHCHCHH (EHz-CH9HCH i Substituted ullylcerbinyl aluminum halide Substituted l-alkene and substituted methylmoiety and substituted cyclopropylcnreyelopropune (hydrolysis product from colbinyl aluminum halide moiety umn 3) CHaCl CHFCHCHCHS 3-methyl-1-butene.

1,2-dimethy1cyc1opropane.

3-methyl-1-undecene.

1-methyl2-octyloyclopropaue.

3-methyl-4-eyclopentyl-l-butene.

l-methyl-2-cyc10pentylcerbinyl-cyclopropane.

0 H2 CH (CH2) 4Br CH 3 2,3-dimethyl-L8-nonadiene. CHz=( J CH(CH;) CH=CH2 21 H2 film (IJHa ,1-d1methyl-2-(hex-5-enyl)-cyelopropane.

CHzC-CH(CH2)4CH=CH z tlBr CH H3 3,3-dimethyl-l,8-nonadlene.

CH=CHO (CH2)4CH=CH2 3 1,2-dimethyl-2-(hex-B-enyl)-eyc1opm ane.

CH2- CH-C (CHz)4 CH=CH2 2 iiB r CH2 4 C H =CH CH2 F CH3 2,3-dimethyl-1,5-hexadiene. CH2=CCHCH2CH=CH2 al CH2 all CH3 1,1-dimethyl-2-allylcyclopropane.

CH2( 3-CHCH2CH=CH2 i ll F CH2 CH3 3,3-dimethy1-1,G-hexadiene.

CHFCHC CH2CH=CH2 6H2 l1 F s s CH 1,2-dimethyl-2-allylcyclopropane.

Table Continued Aiumina-cyclopent- Primary aliphatic monohaiide 3-ene moiety reactant binyi aluminum halide moiety ozHi C HmlI CHzalBr i CHgHCHZCHEBI cmcmcmcum CHzalBr (CHQzCHCHzCHz GH2E1BI (CHghCHCHnCHz -GHaalBr @wm m Substituted allylcarbinyl aluminum halide Substituted l-nlkeno and substituted methylmoiety and substituted cyclopropyicarcyciopropane (hydrolysis product from column 3) (CHahCH Hz h Aluminacyclopent- Primary aliphatic monohaiide 3-ene moiety reactant The organoaluminum halides of this invention are generally soluble in conventional hydrocarbon solvents such as benzene 75 or toluene, and since they are usually formed in the presence Table Continued Substituted allylcarbinyl aluminum halide Substituted l-alkene and substituted methylmoiety and substituted binyl aluminum halide moiety OHzBlBr amon -Q alBr nlBr CH;

alBr

CaHs alBr CH CIMHBD CH2=CHECH CzHs CHr-CHzCH 0 CzH5 ! H2 alBr a lBr C 2 eyclopropylcarcyclopropane (hydrolysis product from column 3) of a Lewis base such as an ether they normally are complexed therewith. These complexes, especially when the Lewis base is a tertiary amine, dialkyl ether, cycloparafiinic monoether having a six membered ring or cycloparafiinic diether having a five or six membered ring, constitute preferred embodiments of this invention. It is convenient and preferred to synthesize these organoaluminum halides in 1,4-dioxane and thus the 1,4-dioxanate complexes of the organoaluminum halides of this invention constitute a preferred embodiment.

As is evident from the table presented above, a wide variety of primary organic monohalides may be used as reactants in forming the novel organoaluminum halides of this invention. These reactants may be depicted by the general formula where R is a suitable organic radical and X is halogen (F, Cl, Br, I). The preferred primary aliphatic monohalides of this type are the primary hydrocarbyl monohalides, especially those in which the halogen atom is chlorine, bromine or iodine. Nevertheless, this reactant may be substituted with innocuous substituents--i.e., substituents which do not prevent the desired reaction(s) from occurring. For example, the presence in the primary organic monohalide of additional halogen atoms attached to tertiary carbon atoms or to an aromatic ring is not harmful as these additional halogen atoms will not adversely affect the reaction. By the same token, the presence in the organic portion of the molecule (R in the formula presented in this paragraph) of trialkylsilyl, triarylsilyl, and like trihydrocarbyl silane groups; ether oxygen atoms (e.g., alkoxy, aryloxy, and related groups); or thioether sulfur atoms is permissible, thesOe constituting typical examples of innocuous substitutents in the sense used herein. Accordingly, the reaction may involve use of such compounds as the methyl halides, ethyl halides, n-butyl halides, isobutyl halides, 2-ethylhexyl halides, n-octadecyl halides, crotonyl halides, 8-haloloctenes, 8halo-2-octenes, 8-halo-3-octenes, 8-halo-4-octenes, 7-halo-l-heptynes, benzyl and phenethyl halides (including those in which the ring carries substituents such as halogen, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, silyl groups, etc.), primary monohaloethers and thioethers and the like. It will be seen that these various reactants are characterized by containing a monohalocarbinyl group.

Particularly preferred primary aliphatic monohalide reactants include methyl bromide, methyl chloride, methyl iodide, allyl chloride, allyl bromide, allyl iodide, benzyl chloride, benzyl bromide, benzyl iodide, propargyl chloride, propargyl bromide and propargyl iodide. It will be seen that the use of the methyl halide results in R in Formulas (I) and (II) above being hydrogen. Similarly the allyl halides result in R in Formulas (I) and (II) being vinyl whereas it is phenyl when using the benzyl halides. The propargyl halides give rise to the formation of compounds in which R of Formulas (l) and (II) is ethynyl.

Reaction between the aluminacyclopent-3-ene moiety and the primary aliphatic monohalide coreactive therewith is conducted in the presence of a Lewis base having suitable chemical stability under the reaction conditions being utilized. In most cases this Lewis base will be employed as the principal reaction solvent--i.e., the reaction will be conducted in the Lewis base selected for use. However, if desired, the reaction may be effected in a suitable inert hydrocarbon medium (e. g., paraffinic or aromatic hydrocarbon solvents such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylenes, and the like) provided a suitable amount of the Lewis base is also present in the reaction system. Ordinarily the system should contain at least l-Z mols of Lewis base per equivalent of aluminacyclopent-3-ene moiety employed. Particularly convenient Lewis bases for use in the process are tertiary amines (e.g., trimethyl amine, dirnethylethyl amine, triethyl amine, tributyl amine, triphenyl amine, tribenzyl amine, benzyldimethyl amine, N-methyl morpholine, N,N- diethyl aniline, N,N,N',N'-tetramethyl methylene diamine, N,N,N',N'-tetramethyl ethylene diamine, pyridine, N-methyl pyrrolidine, triethylene diamine, quinuclidine, and the like); dialkyl ethers (e,g., dimethyl ether, diethyl ether, diisopropyl ether, methylisoamyl ether, dibutyl ether, dihexyl ether and the like); cycloparaffinic monoethers having a six membered ring (e.g., tetrahydropyran-pentamethylene oxide-and ring alkylated derivatives thereof); and cycloparafiinic diethers having a five or six membered ring (e.g., 1,4-di0xane, 1,3- dioxolane, 2-methyl-2-ethyl-1,3-dioxolane; and the like); and other similar substances which tend not to be excessively cleaved in the reaction, such as dicyclohexyl ether, dibenzyl ether, and the like.

The relative proportions of the reactants and reaction diluents do not appear to be critical as long as there is present a sufiicient amount of each reactant to participate in the reaction. However, for best results it is desirable to employ at least a stoichiometric quantity of the primary aliphatic monohalide per equivalent of aluminacyclopent-Ii-ene moiety present in the system. When the monohalide is introduced in the vapor state it is convenient to employ an excess relative to the aluminacyclopent-Ii-ene moiety.

In conducting the process for producing the organo aluminum halides of this invention, elevated temperatures are employed. Generally, temperatures within the range of about to about 180 C. will be found satisfactory, temperatures within the range of about to about C. being preferred. Naturally, one should select a reaction temperature at which the reaction proceeds at a satisfactory rate without encountering excessive adverse side reactions such as thermal decomposition, undesired cleavage reactions, undesired double bond isomerizations or the like.

Ordinarily the reaction will be conducted at atmospheric pressure or at the ambient pressures which prevail when con ducting the reaction in a closed reaction vessel. However when using some of the lower boiling primary organic halide reactants, it is desirable to conduct the reaction at a high enough pressure to insure intimate contact between the reactants in the system. Thus, pressures up to about 50 atmospheres or more may be employed where desirable or convenient.

In performing the hydrolysis reaction in accordance with this invention, use may be made of a wide variety of suitable hydrolysis reagents. Thus, use may be made of water, dilute mineral acids (e.g., HCl, H 80 H PO etc.), dilute aqueous bases (e.g., dilute KOH, dilute NaOH, aqueous NH OH, etc.), aqueous solutions of ammonium chloride, and the like. Hydrolysis temperatures are normally within the range of from about l0 C. up to about 100C. although any suitable temperature may be selected. As noted above, the temperature employed in the hydrolysis reaction should take into consideration the discovery that low temperatures within this range tend to provide an increased proportion of the substituted olefin relative to the substituted cyclopropane. Conversely as the temperatures are increased within this range there is a tendency for the proportion of the substituted cyclopropane to be increased at the expense of the substituted olefin. Thus, it will be found helpful to perform a few pilot experiments to ascertain the optimum hydrolysis temperature for use in any given situation.

In order to still further appreciate the practice and advantages of this invention reference should be had to the following illustrative examples.

EXAMPLE I Reaction Between the 3-Methylaluminacyclopent-3-ene Moiety and Allyl Bromide Followed by Hydrolysis Treatment of 36 mmoles of 3-methylaluminacyclopent-3- ene moiety in 50 ml. of 1,4-dioxane with 58 mmoles of allyl bromide for 2 hours at 135 C. followed by vacuum removal of the solvent at room temperature resulted in a non-volatile liquid. The liquid was dissolved in ml. diethyl ether and hydrolyzed at 0 C. using H O followed by dilute HCl. Workup consisted of washing several times with H O, once with dilute Nal-ICO then with H 0, and drying with MgSO The solvent was carefully removed by evaporation through an 18 inch Vigreux column using an H O bath with a maximum temperature of 65 C. Careful distillation resulted in the isolation of a main cut (2.6g) boiling at 101l03 C. Four compounds were present by vpc analysis (B,;9-oxydipropionitrile column, 20 X 54.") in addition to a small amount of diethyl ether and dioxane. Mass spectrographic analysis of the four compounds showed them to be isomeric C l-l hydrocarbons. After removal of all of the diethyl ether and most of the dioxane by preparative vpc techniques, the four compounds were resolved into two fractions by the B,B'-oxydipropionitrile column. The first fraction contained the most material and NMR analysis showed that this fraction contained a mixture of 1-allyl-2,2-dimethylcyclopropane and l-allyl-l,2-dimethylcyclopropane with the latter being present only to a small extent. The second fraction consisted of a mixture of 2,3- dimethyl-l,5-hexadiene and 3,3-dimethyl-l ,S-hexadiene. It was found that these four compounds had been formed in the following proportions:

l-allyl-2,2-dimethylcyclopropane 70% l-allyl-l ,Z-dimethylcyclopropane 2,3-dimethyll ,S-hexadiene 3,3-dimethyll ,S-hexadiene 5% These C l-l hydrocarbons were obtained in at least 66 percent yield based on the 3-methyla.luminacyclopent-3-ene moiety. The organo aluminum halides produced in the course of this experiment contained the moieties:

Reaction Between the 3-Methylaluminacyclopent-B-ene Moiety and Allyl Chloride Followed by Hydrolysis The procedure of Example I was repeated under essentially the same conditions except that a corresponding amount of allyl chloride was employed as the halide reactant. The same four C li products were obtained. However in this instance the product contained somewhat less than 25 percent of the dimethylallyl cyclopropanes and somewhat more than 75 percent of the dimethyl-] ,5-hexadienes.

EXAMPLE III Reaction Between the 3-Methylaluminacyclopent-3-ene Moiety and Allyl Iodide Followed by Hydrolysis Repetition of the procedure of Example I utilizing allyl iodide as the monohalide reactant produced the same four C H products. In this case 41 percent of the total product was the dimethylallylcyclopropane isomers and 59 percent the dimethyl-1,5-hexadienes.

Since in all of the experiments of Examples l-lll inclusive the reaction and work-up conditions were quite similar, it can be seen that the use of the allyl bromide definitely tends to lead to cyclic products whereas with the allyl chloride and allyl iodide the non-cyclic products predominate.

EXAMPLE IV Reaction Between the 3-Methylaluminacyclopent-3-ene Moiety and Benzyl Chloride Followed by Hydrolysis Reaction of benzyl chloride with the 3-methylaluminacyclopent-S-ene moiety in 1,4-dioxane at 135 C. followed by hydrolysis resulted in the formation of a mixture containing about 77 percent 2,3-dimethyl-4-phenylbutene, about 15 percent of 3,3-dimethyl-4-phenyl-l-butene, the balance being predominantly cyclopropyl C I-i isomers (benzyldimethylcyclopropane isomers).

EXAMPLE v Reaction Between the 3 Methylaluminacyclopent-3-ene Moiety and Benzyl Bromide Followed by Hydrolysis When benzyl bromide was allowed to react with the 3- methylalurninacyclopent-Ii-ene moiety in 1,4-dioxane at C., the hydrolysis products contained approximately 45 percent of two isomeric benzyl-substituted cyclopropanes (mostly l-benzyl-2,Z-dimethylcyclopropane along with lbenzyl-l,Z-dimethylcyclopropane) and about 55 percent of open chain isomers, viz., l-phenyl-2,3-dimethyl-l-butene and l-phenyl-3 ,3-dimethyll -butene, with the former predominatmg.

A comparison of the results of Examples IV and V shows that the use of the benzyl chloride resulted in the formation of the open chain isomers almost exclusively. On the other hand, benzyl bromide gave 55 percent of the open chain isomers and 45 percent of the substituted cyclopropanes. Consequently this is another indication that the bromide reactants tend to produce a higher proportion of the substituted cyclopropane derivatives than do the chloride reactants.

EXAMPLE VI Reaction Between the 3-Methylaluminacyclopent-3-ene Moiety and Methyl Bromide Followed by Hydrolysis Methyl bromide and 3-methylaluminacyclopent-3-ene moiety were heated together at 1 10 C. for 12 hours. Aliquots of the reaction product were hydrolyzed at difierent temperatures and isomeric C H compounds were liberated. These were identified by NMR and vpc retention as 1,1,2-trimethylcyclopropane and 2,3-dimethyl-l-butene, with perhaps a small quantity of 3,3-dimethyl-1-butene being present. These had been produced in a yield considerably above 50 percent based on the 3-methylaluminacyclopent-3-ene moiety. From these hydrolysis studies it was discovered that the relative amounts of the open chain isomer and the cyclic isomer liberated was dependent on the temperatures of the hydrolysis mixture as shown by the following tabulation:

Approximate Percentage of Hydrolysis l,l,2-Trimethyl- Percentage of Temperature cyclopropane 2,3-Dimethyll -butene 0C. 30 7O 25C. 52 48 60-70C. 77 23 These results indicate that the ratio of open chain to cyclopropyl products can be controlled since it is temperature dependent, the cyclopropyl product predominating at the higher temperature.

Illustrative allylcyclopropanes of this invention (Formula III above) include:

l-allyl-2-methylcyclopropane l-allyl-2,Z-dimethylcyclopropane l-allyl- 1 ,Z-dimethylcyclopropane l-allyl-l ,2,2-trimethylcyclopropane l -allyl-2-ethyl-2-methylcyclopropane l -a1lyl- 1 -ethyl-2-methylcyclopropane l-allyl-2-octyl-2-methylcyclopropane l-allyl-2-(4-methyl-3-pentenyl)-2-methylcyclopropane Exemplary benzyl-substituted cyclopropanes of this invention (Formula IV above) are:

l-benzyl-2-methylcyclopropane l-( 2,5-dichlorobenzyl )-2-methylcyclopropane 1 4-butoxybenzyl )-2-methylcyclopropane l-(4-methylbenzyl)-2,2-dimethylcyclopropane l -benzyl-1 ,2,2-trimethylcyclopropane l 4-bromobenzyl )-2-ethyI-Z-methylcyclopropane 1 -benzyl-2-hexyl-2-methylcyclopropane l-benzyl-2-( 4-methyl-3-pentenyl( -2-methylcyclopropan e Although this invention has been described with reference to the use of primary aliphatic monohalides as the reactant it may be found possible to use secondary aliphatic monohalides, especially where the halogen atom is not excessively hindered sterically and where the halogen atom is activated through proximity to a suitable functional group such as an ether oxygen atom.

Among the uses for the organoaluminum halide products of this invention is their suitability as catalysts for synthesis reactions. For example, these products may be used in forming catalyst systems to be employed in the same general fashion as the conventional Ziegler and Natta catalyst systems. By way of example, these organoaluminum halides may be used in conjunction with conventional transition metal containing catalyst ingredients (e.g., the halides, alkoxides, or chelates of titanium, zirconium, vanadium or the like) in much the same way as alkyl aluminum compounds are now used. Polymers which may be produced in this manner include polyethylene, polypropylene, ethyl-propylene copolymers and terpolymers, poly-4-methylpentene-1, polyvinylchloride and other olefin polymers and synthetic rubbers or elastomers.

Another important use for the organoaluminum halides of this invention is to subject them to controlled oxidation with air, oxygen or air enriched with gaseous oxygen whereby new classes of organic aluminum halides are produced. By way of example, oxidation (air, C., 1 hour, in 1,4-dioxane) of compounds of the general formula gives rise to the formation of compounds of the formula:

wherein R, R and R" are the same or different and are hydrogen or hydrocarbyl groups generally containing up to about 18 carbon atoms each; R" is a hydrocarbon group having up to about 18 carbon atoms (most preferably a lower alkyl gro p); and X is a halogen atom, preferably Cl, Br, or 1.

Similarly controlled oxidation of a compound of the formu- I XAl-CHgC-CCH:R

gives rise to the formation of compounds of the formula:

RI RI! XAlOCH C -CHQR O RIII 0 H2 (VI) wherein the reaction conditions and the identifications of R, R, R" and R'" and X are as set forth with reference to the products of Formula (V) above.

Hydrolysis of the compounds of Formulas (V) and (VI) using conditions of the type described above results in the formation and liberation of carbinols having the corresponding skeletal configurations. Thus, hydrolysis of the compounds of Formula (V) yields substituted 3-buten-l-ols:

and hydrolysis of compounds of the Formula (Vl) produce substituted cyclopropylcarbinols:

wherein R, R and R have the meanings assigned to them above. These substituted cyclopropylcarbinols are of particular interest in that they serve as intermediates for the synthesis of a variety of novel and useful products. For example, they may be esterified with carboxylic acids to produce esters having unusual properties. In addition, they may be reacted with PCI;,, POCl and PSCL, to give phosphite (phosphonate), phosphate and thionophosphate esters having interesting properties. For example, these phosphorus esters may find use as insecticides, fungicides, extreme pressure additives, ignition control additives for gasoline, lubricating oil additives, flame retardants, and the like.

I claim 1. An organoaluminum compound having bonded to an aluminum atom a halogen atom and an allylcarbinyl group of the formula wherein R, R and R are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by a hydrocarbyl group.

2. The composition of claim 1 wherein R and R are selected from the group consisting of hydrogen and lower alkyl groups.

3. The composition of claim 1 wherein the halogen atom is chlorine, bromine, or iodine.

4. The composition of claim 1 wherein the halogen atom is chlorine, bromine, or iodine and wherein R and R are selected from the group consisting of hydrogen and lower alkyl groups.

5. The composition of claim 1 wherein the halogen atom is chlorine.

6. The composition of claim 1 wherein R is hydrogen, phenyl or vinyl.

7. The composition of claim 1 wherein the halogen atom is chlorine, wherein R is vinyl and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

8. The composition of claim 1 wherein the halogen atom is bromine, wherein R is vinyl and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

9. The composition of claim 1 wherein the halogen atom is iodine, wherein R is vinyl and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

10. The composition of claim 1 wherein the halogen atom is chlorine, wherein R is phenyl and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

11. The composition of claim 1 wherein the halogen atom is bromine, wherein R is phenyl and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

12. The composition of claim 1 wherein the halogen atom is bromine, wherein R is hydrogen and wherein R and R are selected from the group consisting of hydrogen and lower alkyl groups.

13. The composition of claim 1 wherein the compound is complexed with a Lewis base.

14. An organoaluminum compound having bonded to an aluminum atom a halogen atom and a cyclopropylcarbinyl group of the formula wherein R, R and R" are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by a hydrocarbyl group.

15. The composition of claim 14 wherein R and R are selected from the group consisting of hydrogen and lower alkyl groups.

16. The composition of claim 14 wherein the halogen atom is chlorine, bromine, or iodine.

17. The composition of claim 14 wherein the halogen atom is chlorine, bromine, or iodine and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

18. The composition of claim 14 wherein the halogen atom is bromine.

19. The composition of claim 14 wherein R is hydrogen, phenyl or vinyl.

20. The composition of claim 14 wherein the halogen atom is chlorine, wherein R is vinyl and wherein R and R are selected from the group consisting of hydrogen and lower alkyl groups.

21. The composition of claim 14 wherein the halogen atom is bromine, wherein R is vinyl and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

22. The composition of claim 14 wherein the halogen atom is iodine, wherein R is vinyl and wherein R and R are selected from the group consisting of hydrogen and lower alkyl groups.

23. The composition of claim 14 wherein the halogen atom is chlorine, wherein R is phenyl and wherein R and R are selected from the group consisting of hydrogen and lower alkyl groups.

24. The composition of claim 14 wherein the halogen atom is bromine, wherein R is phenyl and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

25. The composition of claim 14 wherein the halogen atom is bromine, wherein R is hydrogen and wherein R and R" are selected from the group consisting of hydrogen and lower alkyl groups.

26. The composition of claim 14 wherein the compound is complexed with a Lewis base.

27. A process which comprises reacting a primary hydrocarbyl monohalide with an organoaluminum compound containing an aluminacyclopent-3-ene moiety wherein the third valence bond of the aluminum atom is satisfied by a hydrocarby] group to produce a. An organoaluminum compound having bonded to an aluminum atom a halogen atom and an allylcarbinyl group of the formula wherein R, R and R are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by a hydrocarbyl group; or

b. An organoaluminum compound having bonded to an aluminum atom a halogen atom and a cyclopropyl-carbinyl group of the formula wherein R, R and R" are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by a hydrocarbyl group; or

0. An organoaluminum compound as defined in (a) and an organoaluminum compound as defined in (b).

28. An organoaluminum compound having bonded to an aluminum atom a halogen atom and an allylcarbinyl group of the formula wherein R, R and R" are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by an innocuous substituent, said substituent being a hydrocarbon substituent or a hydrocarbon substituent containing an aluminum atom.

29. An organoaluminum compound having bonded to an aluminum atom a halogen atom and a cyclopropylcarbinyl group of the formula wherein R, R and R" are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by an innocuous substituent, said substituent being a hydrocarbon substituent or a hydrocarbon substituent containing an aluminum atom.

30. A process which comprises reacting a primary hydrocarbyl monohalide with an organoaluminum compound containing an aluminacyclopent-Zi-ene moiety in which the third bond of the aluminum atom is satisfied by an innocuous substituent to produce an organoaluminum compound having bonded to an aluminum atom (i) a halogen atom, (ii) an innocuous substituent, and (iii) either (a) an allylcarbinyl group of the formula wherein R, R and R" are the same or different and are hydrogen or hydrocarbyl groups; or (b) a cyclopropylcarbinyl group of the formula wherein R, R and R are the same or different and are hydrogen or hydrocarbyl groups, said substituent being a hydrocarbon substituent or a hydrocarbon substituent containing an aluminum atom.

31. The process of claim 27 conducted in a liquid reaction medium in the presence of a tertiary amine, a dialkyl ether, a cycloparaffinic monoether having a six-membered ring, or a cycloparaffinic diether having a fiveor six-membered ring and wherein the monohalide is an ally] halide, a benzyl halide, or a methyl halide and wherein the halogen atom thereof is chlorine, bromine or iodine.

32. The process of claim 27 wherein the monohalide is a chloride, bromide, or iodide.

33. The process of claim 27 wherein the predominant product is a compound as defined in subparagraph (a) thereof.

34. The process of claim 27 wherein the product is enriched in a compound as defined in subparagraph (a) thereof and wherein the monohalide is a chloride.

35. The process of claim 27 wherein the predominant product is a compound as defined in subparagraph (b) thereof.

36. The process of claim 27 wherein the product is enriched in a compound as defined in subparagraph (b) thereof and wherein the monohalide is a bromide.

37. The process of claim 27 wherein the monohalide is an allylic monohalide.

38. The process of claim 27 wherein the monohalide is an ally! halide, a benzyl halide, or a methyl halide and wherein the halogen atom thereof is chlorine, bromine, or iodine.

39. The process of claim 27 conducted in the presence of a Lewis base.

40. The process of claim 27 conducted in a liquid reaction medium and in the presence of a tertiary amine, a dialkyl ether, a cycloparaffinic monoether having a six-membered ring, or a cycloparaffinic diether having a fiveor six-membered ring.

41. The process of claim 27 conducted in l,4-dioxane.

I I? t l 

2. The composition of claim 1 wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 3. The composition of claim 1 wherein the halogen atom is chlorine, bromine, or iodine.
 4. The composition of claim 1 wherein the halogen atom is chlorine, bromine, or iodine and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 5. The composition of claim 1 wherein the halogen atom is chlorine.
 6. The composition of claim 1 wherein R is hydrogen, phenyl or vinyl.
 7. The composition of claim 1 wherein the halogen atom is chlorine, wherein R is vinyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 8. The composition of claim 1 wherein the halogen atom is bromine, wherein R is vinyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 9. The composition of claim 1 wherein the halogen atom is iodine, wherein R is vinyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 10. The composition of claim 1 wherein the halogen atom is chlorine, wherein R is phenyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 11. The composition of claim 1 wherein the halogen atom is bromine, wherein R is phenyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 12. The composition of claim 1 wherein the halogen atom is bromine, wherein R is hydrogen and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 13. The composition of claim 1 wherein the compound is complexed with a Lewis base.
 14. An organoaluminum compound having bonded to an aluminum atom a halogen atom and a cyclopropylcarbinyl group of the formula wherein R, R'' and R'''' are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by a hydrocarbyl group.
 15. The composition of claim 14 wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 16. The composition of claim 14 wherein the halogen atom is chlorine, bromine, or iodine.
 17. The composition of claim 14 wherein the halogen atom is chlorine, bromine, or iodine and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 18. The composition of claim 14 wherein the halogen atom is bromine.
 19. The composition of claim 14 wherein R is hydrogen, phenyl or vinyl.
 20. The composition of claim 14 wherein the halogen atom is chlorine, wherein R is vinyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 21. The composition of claim 14 wherein the halogen atom is bromine, wherein R is vinyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 22. The composition of claim 14 wherein the halogen atom is iodine, wherein R is vinyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 23. The composition of claim 14 wherein the halogen atom is chlorine, wherein R is phenyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 24. The composition of claim 14 wherein the halogen atom is bromine, wherein R is phenyl and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 25. The composition of claim 14 wherein the halogen atom is bromine, wherein R is hydrogen and wherein R'' and R'''' are selected from the group consisting of hydrogen and lower alkyl groups.
 26. The composition of claim 14 wherein the compound is complexed with a Lewis base.
 27. A process which comprises reacting a primary hydrocarbyl monohalide with an organoaluminum compound containing an aluminacyclopent-3-ene moiety wherein the third valence bond of the aluminum atom is satisfied by a hydrocarbyl group to produce a. An organoaluminum compound having bonded to an aluminum atom a halogen atom and an allylcarbinyl group of the formula wherein R, R'' and R'''' are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by a hydrocarbyl group; or b. An organoaluminum compound having bonded to an aluminum atom a halogen atom and a cyclopropyl-carbinyl group of the formula wherein R, R'' and R'''' are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by a hydrocarbyl group; or c. An organoaluminum compound as defined in (a) and an organoaluminum compound as defined in (b).
 28. An organoaluminum compound having bonded to an aluminum atom a halogen atom and an allylcarbinyl group of the formula wherein R, R'' and R'''' are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by an innocuous substituent, said substituent being a hydrocarbon substituent or a hydrocarbon substituent containing an aluminum atom.
 29. An organoaluminum compound having bonded to an aluminum atom a halogen atom and a cyclopropylcarbinyl group of the formula wherein R, R'' and R'''' are the same or different and are hydrogen or hydrocarbyl groups, the third bond of the aluminum atom being satisfied by an innocuous substituent, said substituent being a hydrocarbon substituent or a hydrocarbon substituent containing an aluminum atom.
 30. A process which comprises reacting a primary hydrocarbyl monohalide with an organoaluminum compound containing an aluminacyclopent-3-ene moiety in which the third bond of the aluminum atom is satisfied by an innocuous substituent to produce an organoaluminum compound having bonded to an aluminum atom (i) a halogen atom, (ii) an innocuous substituent, and (iii) either (a) an allylcarbinyl group of the formula wherein R, R'' and R'''' are the same or different and are hydrogen or hydrocarbyl groups; or (b) a cyclopropylcarbinyl group of the formula wherein R, R'' and R'''' are the same or different and are hydrogen or hydrocarbyl groups, said substituent being a hydrocarbon substituent or a hydrocarbon substituent containing an aluminum atom.
 31. The process of claim 27 conducted in a liquid reaction medium in the presence of a tertiary amine, a dialkyl ether, a cycloparaffinic monoether having a six-membered ring, or a cycloparaffinic diether having a five- or six-membered ring and wherein the monohalide is an allyl halide, a benzyl halide, or a methyl halide and wherein the halogen atom thereof is chlorine, bromine or iodine.
 32. The process of claim 27 wherein the monohalide is a chloride, bromide, or iodide.
 33. The process of claim 27 wherein the predominant product is a compound as defined in subparagraph (a) thereof.
 34. The process of claim 27 wherein the product is enriched in a compound as defined in subparagraph (a) thereof and wherein the monohalide is a chloride.
 35. The process of claim 27 wherein the predominant product is a compound as defined in subparagraph (b) thereof.
 36. The process of claim 27 wherein the product is enriched in a compound as defined in subparagraph (b) thereof and wherein the monohalide is a bromide.
 37. The process of claim 27 wherein the monohalide is an allylic monohalide.
 38. The process of claim 27 wherein the monohalide is an allyl halide, a benzyl halide, or a methyl halide and wherein the halogen atom thereof is chlorine, bromine, or iodine.
 39. The process of claim 27 conducted in the presence of a Lewis base.
 40. The process of claim 27 conducted in a liquid reaction medium and in the presence of a tertiary amine, a dialkyl ether, a cycloparaffinic monoether having a six-membered ring, or a cycloparaffinic diether having a five- or six-membered ring.
 41. The process of claim 27 conducted in 1,4-dioxane. 